EP3525924B1 - Detergent composition having a flow limit - Google Patents

Description

The present invention is in the technical field of liquid surfactant compositions and relates to the generation of a yield point in said liquid surfactant compositions. The present invention further relates to a process for the preparation of a microemulsion of a non-polymeric organic thickener and the preparation of said liquid surfactant compositions with yield point using said microemulsion.

For incorporation into liquid surfactant compositions, in particular detergents or cleaning agents, there are either those ingredients which dissolve in the liquid phase of the agent or which can be correspondingly homogeneously suspended undissolved. In the case of insoluble ingredients, a stable, homogeneous suspension is necessary for the function and aesthetics of the detergent or cleaning agent. Sedimented solid particles can clump and, when used, lead to local overconcentrations of the ingredient and thus to uneven dosing per wash load. Visible clumps, greasy deposits or deposits of the solid ingredient on e.g. a transparent wall of the storage vessel also mean an aesthetic flaw.

The incorporation of a few, possibly colored, solid particles that can be recognized by the naked human eye in suspension in a transparent or translucent, liquid phase as individualized particles are often referred to as speckles. Corresponding particles have a corresponding particle size for this purpose and offer the consumer an aesthetic appeal. Microcapsules are also solid ingredients and include any type of capsule known to the person skilled in the art, but in particular core-shell capsules and matrix capsules. Matrix capsules are porous molded bodies that have a structure similar to a sponge. Core-shell capsules are shaped bodies that have a core and a shell. However, all of these solid particles, in particular the speckles, tend to sediment in liquid surfactant compositions.

The sedimentation of particles from the suspension is usually avoided through the use of surfactant compositions with a flow limit. A flow limit can be generated through the selection of special surfactant combinations, usually in the presence of an electrolyte salt, through the establishment of a lamellar phase. The use of selected polymeric thickeners is also conceivable for generating a flow limit.

In particular, surfactant compositions with a high surfactant concentration are difficult to provide with a flow limit in the range from 0.01 to 5 Pa. By using lyotropic In liquid-crystalline mesophases, a flow limit that is too high is usually achieved with a high surfactant concentration. In such a case, the flow behavior is inhomogeneous (so-called "lumpy" flow). Furthermore, if the flow limit is too high, the suspended particles adhere to the wall of the storage vessel for the surfactant composition. If polymeric thickeners are used to form the flow limit, this sometimes succeeds with a high surfactant concentration using a very large amount of the polymeric thickener, and often it does not succeed at all. Large amounts of thickener impair the cleaning performance of surfactant compositions, which can also lead to graying of the textile, especially when treating textiles.

The pamphlets WO 2011/120772 and WO 2011/120799 relate to the production of liquid detergents with a flow limit, an already structured premix with a flow limit being prepared beforehand and mixed with an aqueous surfactant composition.

The pamphlet WO 2011/031940 relates to a structuring agent for liquid and gel detergents, which contains 2 to 10% by weight of crystals of a glyceride, preferably hydrogenated castor oil, and 2 to 10% by weight of alkanolamine and 5 to 60% by weight of the anion of an anionic surfactant, but none contains inorganic cations.

The pamphlet WO 2002/40627 relates to aqueous liquid detergents which contain an agent with low solubility substantive for textiles, a crystalline stabilizing agent containing hydroxyl groups and a non-surfactant, dissolved ingredient. The premix used to produce the liquid detergent contains water, surfactant and 0.1 to 5% by weight of said thickener in crystalline form as a solid.

The pamphlet WO 2005/012475 also relates to liquid detergents with a flow limit which are produced by using an already structured premix containing a hydroxyl group-containing thickener in crystalline form.

The pamphlet WO 2015/200062 relates to a premix for the production of liquid detergents with a flow limit, which is already structured by a crystalline hydroxyl-containing thickener and additionally contains an alkyl sulfate surfactant. DE 10129517 and US 4472291 disclose microemulsions containing thickeners. the US 2005/239674 discloses a cleaning agent containing inorganic or organic thickeners.

According to the disclosure of the cited publications, the above-described premixes of the prior art are liquid, viscous and already structured. Nevertheless, they do not contain a thickener with a structuring effect, which means that either a lot of water or a lot of foreign surfactant is carried into the final liquid detergent due to the premix during the production of the liquid detergent. The person skilled in the art will find out that the premixes prepared according to the manufacturing instructions of the state of the art involve inhomogeneous incorporation of the thickener and are therefore difficult to dose. Liquid detergents which are produced with the premixes of the prior art have a precipitate and have no flow limit.

The present invention is based on the object of providing liquid surfactant compositions, in particular detergents or cleaning agents with excellent washing or cleaning power, which have a flow limit and in which solid particles (in particular speckles) can be homogeneously suspended so that they are stable in storage conditions Suspension remain.

For this purpose, any liquid surfactant composition without a flow limit should be structured by adding a thickener, without the surfactant system of the resulting liquid surfactant composition with flow limit undergoing any significant change in comparison to the unstructured surfactant composition due to the addition of a liquid premix containing the structuring thickener. On the one hand, the premix used is intended to introduce as few additional foreign surfactants as possible into the liquid surfactant composition. On the other hand, the premix used for structuring should be used in small quantities.

In addition, it was an object to provide a production method for said liquid surfactant compositions in which - in particular in a continuous production process - a thickener can be easily metered and forms as few deposits as possible in the production plant.

It has surprisingly been found that liquid surfactant compositions with a yield point can be produced by using a microemulsion of a non-polymeric thickener. If these surfactant compositions are used as a continuous phase of a suspension, the solid phase is homogeneously and stably suspended therein. In addition, thermodynamically multiphase surfactant formulations can be prevented from macroscopic separation. By adding said microemulsion, a formulation which, like an emulsion, consists of several immiscible liquid phases, can be converted into a storage-stable, macroscopically single-phase and homogeneous product.

The microemulsion used to achieve the flow limit is easy to process and dose due to its flowability.

1. a) eine flüssige Phase,
2. b) eine Gesamtmenge von 30,0 Gew.-% bis 95,0 Gew.-% mindestens eines nicht-polymeren, organischen Verdickungsmittels mit einem Molekulargewicht im Bereich von 100 g/mol bis 1500 g/mol als emulgierte Phase,
3. c) eine Gesamtmenge von 2,0 Gew.-% bis 60,0 Gew.-% eines Tensidsystems, enthaltend mindestens ein nichtionisches Tensid.

A first subject of the invention is therefore a microemulsion, each containing based on the total weight of the emulsion

1. a) a liquid phase,
2. b) a total amount of 30.0% by weight to 95.0% by weight of at least one non-polymeric, organic thickener with a molecular weight in the range from 100 g / mol to 1500 g / mol as the emulsified phase,
3. c) a total amount of 2.0% by weight to 60.0% by weight of a surfactant system containing at least one nonionic surfactant.

For the purposes of the invention, for the definition of a number range which should lie “between” two range limits, following general usage, the range limits are not included. Number ranges that are defined from one range limit to another range limit include the range limits.

In general, “at least one”, as used herein, means 1, 2, 3, 4, 5, 6, 7, 8, 9 or more, the information relating to the type of substance mentioned and not the absolute number of molecules.

The surfactant compositions according to the invention obtain their flow limit according to the invention through the use of said microemulsions with non-polymeric, organic thickeners.

The flow limit describes the smallest stress (force per area) above which a plastic material behaves rheologically like a liquid. It is therefore given in Pascal (Pa).

The flow limits of the detergents or cleaning agents were measured with a rotary rheometer from TA Instruments, type AR G2. This is a so-called shear stress controlled rheometer.

Various methods known to the person skilled in the art are described in the literature for measuring a yield point with a shear stress-controlled rheometer.

To determine the flow limits in the context of the present invention, the following procedure was carried out at 20 ° C:
The samples were subjected to a shear stress σ increasing gradually over time in a "stepped flow procedure" in the rheometer. For example, the shear stress can be increased from the smallest possible value (eg 2 mPa) to eg 10 Pa in the course of 10 minutes with 10 points per shear stress decade. The time interval is selected in such a way that the measurement takes place “quasi-statically”, ie that the deformation of the sample can come into equilibrium for any given shear stress value. As a function of this Shear stress, the equilibrium deformation γ of the sample is measured. The deformation is plotted against the shear stress in a double logarithmic plot. If the examined sample has a flow limit, one can clearly distinguish two areas in this plot. Below a certain shear stress there is a purely elastic deformation according to Hooke's law. The slope of the curve γ (σ) (log-log plot) in this area is one. Above this shear stress, the flow area begins and the slope of the curve is suddenly higher. The shear stress at which the curve kinks, i.e. the transition from elastic to plastic deformation, marks the yield point. A comfortable determination of the break point is possible by applying tangents to the two parts of the curve. Samples without a yield point show no characteristic kink in the function γ (σ).

According to the invention, a non-polymeric thickener is understood to mean a compound with a thickening effect which is not obtained by polyreaction of monomers. Monomers are molecules that form a polymer through polyreaction, the latter having repeating units in its molecular structure that result from the monomer. A polymer has at least 10 repeating units resulting from the same monomer in its molecular structure.

A thickener has a thickening effect, and when used in an amount of 0.1% by weight it increases the viscosity of the surfactant composition according to the invention by at least 500 mPas.

In the context of this invention, unless otherwise described, the viscosity is determined with a rotational rheometer (cone-plate (40 mm diameter, 2 ° cone angle)) at 0.5 rpm and 20 ° C.

A substance (e.g. thickener) is organic if it contains carbon atoms and hydrogen atoms bonded to them.

Unless otherwise defined, a substance (e.g. the surfactant composition according to the invention) is a liquid if it is liquid at 25 ° C and 1013 mbar.

Unless otherwise defined, a substance is a solid if it has a melting point of less than 25 ° C at 1013 mbar. For the purposes of the invention, capsules are considered to be solid if they are macroscopically solid at 20 ° C. despite the liquid constituents they may contain.

In the context of the invention, a microemulsion is defined as a dispersion at a defined temperature and 1013 mbar that is homogeneous and transparent with the naked eye, of at least two phases that are liquid at this temperature and 1013 mbar and are immiscible with one another.

Within the homogeneous and transparent single-phase area there are different nanostructures depending on the total surfactant concentration and / or temperature. The structure size decreases with increasing surfactant concentration. With a temperature-dependent application of the structure sizes at a constant surfactant concentration, the continuous domains invert from e.g. water-continuous to oil-continuous (or vice versa). Bicontinuous areas or double-layer structures can also be traversed. Bicontinuous structures are also found in microemulsions. Most microemulsions are clear because their structure size in the nm range is well below the wavelength of visible light. In the context of the present invention, the clarity is also assessed as an indicator of the presence of a microemulsion. According to Winsor, microemulsion systems consisting of a water component, an oil component and a surfactant (also: amphiphile) can be divided into 4 types according to their phase equilibrium.

In a Winsor Type I microemulsion system, the surfactant is primarily soluble in water and in an O / W microemulsion form. It consists of a surfactant-rich aqueous phase (O / W microemulsion) and an excess, but low-surfactant oil phase.

In a Winsor Type II microemulsion system, the surfactant is primarily soluble in an oil phase and in a W / O microemulsion form. It consists of a surfactant-rich oil phase (W / O microemulsion) and an excess, but low-surfactant aqueous phase.

A Winsor Type III microemulsion system is an often bicontinuous microemulsion, also called a middle-phase microemulsion, consisting of a surfactant-rich middle phase which coexists with a surfactant-poor aqueous phase as well as a surfactant-poor oil phase.

A microemulsion system of the Winsor type IV, on the other hand, is a single-phase homogeneous mixture and, in contrast to the Winsor types I to III, which consist of 2 or 3 phases, of which only one phase is a microemulsion, represents a total of a microemulsion.

The microemulsions according to the invention are homogeneous, thermodynamically stable and optically isotropic.

A fabric is considered transparent if, with a layer thickness of 1 cm, the letter "A" (Times New Roman, font size 12 pt.) Positioned 1 cm behind the fabric can be read through the fabric with the naked eye.

According to the invention, a surfactant system consists of at least one amphiphilic compound as a constituent of the microemulsion, the amphiphilic compounds of the surfactant system differing from said thickener and said liquid phase. The surfactant system according to the invention necessarily contains at least one nonionic surfactant as an amphiphilic compound, but can also contain further surfactants in addition.

The surfactant system with at least one nonionic surfactant contained in the microemulsion according to the invention is preferably distinguished by a particularly low interfacial tension compared to the said thickener. Interfacial tensions <5 mN / m, particularly preferably <0.5 mN / m and very particularly preferably <0.05 mN / m are preferred. The surfactant system used according to the invention is generally suitable for forming a microemulsion. Accordingly, “suitable to form a microemulsion”, as used in the context of the microemulsions described herein, means that these microemulsions comprise a surfactant system with the properties described and under the test conditions described below, ie at a temperature in the range from 0 to 100 ° C , preferably 40 to 98 ° C, more preferably 75 to 95 ° C, and a water: oil system with a mass ratio of water: oil of 99: 1 to 9: 1, the oil, for example, a triacylglyceride, such as in particular hydrogenated castor oil , can form a Winsor Type IV microemulsion.

"Fishtail point", as used herein, is to be understood as the maximum extent of the single-phase, optically isotropic microemulsion region towards minimum surfactant concentrations, at which the upper and lower phase boundaries intersect, which delimit the same single-phase region. "Upper phase boundary" and "lower phase boundary" preferably describe the transitions between the microemulsion phase (single-phase microemulsions of the Winsor IV type) and excreted excess phases (two-phase microemulsions of the Winsor I or II type) or other structured phases.

Microemulsions preferred according to the invention contain a surfactant system which has a fishtail point in the range from 0.01% by weight to 80% by weight, preferably 0.1% by weight to 70% by weight, particularly preferably 0.2% by weight. % to 60% by weight.

A reference system is defined to determine the fishtail point and these phase boundaries. The methodology described below relates to ternary or higher grade Mixtures consisting of at least one polar component, usually a polar solvent, here in particular water, at least one non-polar component, usually the thickener which can be used according to the invention in its liquid form (hereinafter always referred to as "oil"), and at least one amphiphilic component, ie here the surfactant or surfactant system. The methods described below can be carried out automatically for each thickener according to the invention.

In a first embodiment of the methodology, the fishtail point is determined as the point of intersection of the phase boundaries as a function of temperature, with the mixing ratios of the surfactant components being kept constant when using a surfactant system composed of several surfactants. The point of intersection of the two phase boundaries becomes isoplethal based on a single-phase system and high surfactant concentrations by varying the temperature and then gradually diluting with a constant water: oil ratio (i.e. in particular a water: oil mass ratio in the range from 99: 1 to 9: 1, wherein the oil is the thickener according to the invention, in particular a triglyceride, particularly preferably hydrogenated castor oil) and redetermination of the phase boundaries by varying the temperature, in particular in a range from 0 to 100 ° C, preferably 40 to 98 ° C, even more preferably 60 to 95 ° C determined. After each temperature adjustment, equilibrium of the composition to be investigated must take place. For a better overview, the respective phase transition points (temperature) are plotted graphically as a function of the total concentration of the surfactants (Y-axis: temperature; X-axis: surfactant concentration; for a given water: oil ratio).

"Approximately" as used herein in relation to numerical values means the numerical value ± 10%, preferably ± 5%.

The microemulsion according to the invention preferably has a temperature between 0 to 100.degree. C., preferably from 40 to 98.degree. C., even more preferably from 60 to 95.degree.

Preferred microemulsions are characterized in that the mean curvature of the amphiphilic film in the single-phase region of the microemulsion in the temperature range 0 to 100 ° C, preferably 40 to 98 ° C, more preferably 60 to 95 ° C, is equal to 0. The mean curvature can be reasonably determined by means of conductivity within the given single-phase area, as for example from Strey ( R. Strey Colloid Polym. Sci. 272, 1005-1019, (1994 )) described.

Preferred ranges for the fishtail point are in the range from 0.01 to 80% by weight total surfactant (X-axis) and 0 to 100 ° C (Y-axis), more preferably 0.1 to 70% by weight total surfactant and 40 to 98 ° C, most preferably 0.2 to 60 wt .-% total surfactant and 60 to 95 ° C. The water: oil mass ratio is preferably a constant value in the range from 99: 1 to 9: 1, the oil preferably being triacylglyceride, in particular hydrogenated castor oil.

For determination, a mixture of oil, then amphiphile (surfactant (s)) and then water is weighed into a gas-tight (glass) vessel (including a Teflon-coated magnetic stir bar) and then stirred in a thermostated water bath until a thermal equilibrium is established. The temperature for the fishtail point is selected above the melting point of the thickener according to the invention, preferably in a range from 0 to 100.degree. C., preferably 40 to 98.degree. C., even more preferably 60 to 95.degree.

As an alternative or in addition to the temperature-dependent determination described above, the fishtail point can also be determined depending on the concentration of the surfactants used in a surfactant system composed of several amphiphiles (for example surfactants). For this purpose, at least one first surfactant C1, whereby this at least one first surfactant can also be a mixture of several surfactants, is presented in a concentration below the fishtail point and a second amphiphile / surfactant at a constant temperature and constant water: oil ratio C2 (which is different from the at least one surfactant C1) is titrated until the entire phase space has been clarified or the maximum concentration determined according to the invention has been reached. After the gradual addition of small amounts of surfactant C2, the respective phase state after the equilibrium has been set is documented, a distinction being made between isotropic single-phase and multiphase states. On the basis of the added amount of surfactant of C2, a transition concentration of the respective surfactant, the total surfactant concentration and the relative ratio of the surfactants to one another can be determined for any surfactant concentration of C1 for each phase transition. For a better overview, the respective phase transition points (temperature) are plotted graphically as a function of the total concentration of the surfactants (Y-axis: concentration C2; X-axis: surfactant concentration C1 + C2; for a given water: oil ratio and temperature). After determining all phase transitions for at least five surfactant concentrations C1, the course of the phase boundaries can be described, whereby it must be ensured that the initial surfactant concentrations are chosen so that the intersection of the phase boundaries is described as closely as possible. In such systems comprising several surfactants, it is preferred that the HLB values of the surfactant / surfactants C1 and the amphiphile / surfactant C2 differ by a value of at most 10, preferably not more than 8, more preferably not more than 5, am most preferred no more than 3.

Microemulsions preferred according to the invention are characterized in that the fishtail point is in the range from 0.01 to 80% by weight of total surfactant (X axis) and 0 to 50% by weight Wt .-% surfactant C2 (Y-axis), more preferably 0.1 to 70 wt .-% total surfactant and 0.01 to 40 wt .-% C2, most preferably 0.2 to 60 wt .-% total surfactant and 0 , 1 to 35 wt% C2. The water: oil mass ratio is preferably a constant value in the range from 99: 1 to 9: 1, the oil preferably being a triacylglyceride, in particular hydrogenated castor oil.

The microemulsion can contain lipophilic or hydrophilic thickeners as a continuous medium. In a bicontinuous microemulsion, the respective thickeners are located either in the oil-rich phase or in the water-rich phase. It is preferred according to the invention if the said thickener is in the oil-rich phase of the microemulsion.

The microemulsion according to the invention is preferably characterized in that the liquid phase and the emulsified phase are present as bicontinuous phases or as layers of an L _α phase, in particular as bicontinuous phases.

A mandatory component of the microemulsion according to the invention is a non-polymeric, organic thickener with a molecular weight in the range from 100 g / mol to 1500 g / mol (in particular from 150 g / mol to 1250 g / mol) as the emulsified phase.

It is preferred according to the invention if the said thickener has a melting point of between 30 ° C. and 100 ° C., in particular between 40 ° C. and 95 ° C., very particularly preferably from 60 ° C. to 90 ° C., at 1013 mbar.

The total amount of said thickener based on the total weight of said microemulsion is 30-95% by weight. It is again preferred if the minimum amount of said thickener is a total amount of at least 40% by weight, very particularly preferably at least 50% by weight.

The at least one low molecular weight, organic thickener which is preferably suitable for the microemulsion according to the invention is selected from hydrogenated castor oil, 12-hydroxyoctadec-9-enoic acid, 12-hydroxystearic acid, a glyceride with at least two 12-hydroxyoctadec-9-enoic acid residues, triricinolein, a glyceride with at least two 12-hydroxystearic acid residues, tris-12-hydroxystearin, 4,6-O-benzylidene _{monosaccharide, C 8} -C ₂₂ -alkylamide derivatives of D-glucosamine, urea derivatives, gemini surfactants (in particular N-lauroyl-L-lysine ethyl ester) or from mixtures thereof.

Likewise, all fatty acids from Gelled Bicontinuous Microemulsions - A New Type of Orthogonal Self-Assembled Systems - by Michaela Laupheimer, Dissertation, 2013, University of Stuttgart, are suitable as at least one low molecular weight, organic thickener.

The microemulsion according to the invention necessarily contains, based on the total weight of the microemulsion, a total amount of 2.0% by weight to 60.0% by weight (preferably a

Total amount from 2% by weight to 50% by weight) of a surfactant system containing at least one nonionic surfactant.

Suitable nonionic surfactants include alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, fatty acid alkanolamides, alkoxylated fatty acid amides, hydroxy mixed ethers, sorbitan fatty acid esters, polyhydroxy fatty acid amides, polyhydroxy fatty acid amides, polyhydroxy fatty acid amides (polyhydroxy fatty acid amides, and mixtures thereof), alkylphenol polyglycol ethers, polyglycol ethers (polyglycol ethers), amine, and mixtures thereof.

R1

für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkylrest,

AO

für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung,

m

für ganze Zahlen von 1 bis 50 stehen.

Particularly suitable nonionic surfactants are fatty alcohol alkoxylates. In various embodiments, the agents therefore contain at least one nonionic surfactant of the formula

R ¹ -O- (AO) mH,

in the

R1

for a linear or branched, substituted or unsubstituted alkyl radical,

AO

for an ethylene oxide (EO) or propylene oxide (PO) group,

m

stand for whole numbers from 1 to 50.

In the above formula, R ^{1 represents} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical having 8 to 20 carbon atoms. Preferred leftovers R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of carbon atoms being preferred are. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols.

AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably for an ethylene oxide group or mixtures of ethylene oxide and propylene oxide units. The index m stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. m is very particularly preferably the numbers 2, 3, 4, 5, 6, 7 or 8.

mit k = 7 bis 19, m = 2, 3, 4, 5, 6, 7, 8, 9 oder 10. Ganz besonders bevorzugte Vertreter sind C_12-18 Fettalkohole mit 7 EO (k = 11-17, m = 7).As the nonionic surfactant is particularly preferably at least one C _8-20 alkyl ether, preferably at least one C _8-20 fatty alcohol alkoxylate containing from 1 to 10 EO and PO is 0 to 10 included. Furthermore, fatty alcohol alkoxylates to be used with very particular preference are compounds of the formula

with k = 7 to 19, m = 2, 3, 4, 5, 6, 7, 8, 9 or 10. Very particularly preferred representatives are C _12-18 fatty alcohols with 7 EO (k = 11-17, m = 7 ).

bevorzugt, in der R¹ für einen geradkettigen oder verzweigten C_6-24-Alkylrest steht; R² bzw. R³ für -CH₃ stehen und die Indizes w, x, y, z unabhängig voneinander für 0 oder ganze Zahlen von 1 bis 10 stehen, wobei mindestens eines von w und y und mindestens eines von x und z nicht 0 ist. Insbesondere sind auch nichtionische Tenside bevorzugt, die einen C_8-20-Alkylrest mit 1 bis 10 Ethylenoxideinheiten und 1 bis 10 Propylenoxideinheiten aufweisen.Preferred further nonionic surfactants are, for example, those which have alternating ethylene oxide (EO) and propylene oxide (PO) units. Among these, surfactants with EO-PO-EO-PO blocks are again preferred, one to ten EO or PO groups being bonded to one another before a block from the other groups follows. Here are nonionic surfactants of the general formula

preferred in which R ^{1 is} a straight-chain or branched C _6-24 -alkyl radical; R ² and R ³ stand for -CH ₃ and the indices w, x, y, z independently of one another stand for 0 or integers from 1 to 10, at least one of w and y and at least one of x and z not being 0 is. In particular, nonionic surfactants which have a C _8-20 -alkyl radical with 1 to 10 ethylene oxide units and 1 to 10 propylene oxide units are also preferred.

Amine oxides, for example, are also suitable as nonionic surfactants. In principle, all amine oxides established in the prior art for these purposes, i.e. compounds which have the formula R ¹ R ² R ³ NO, in which each R ¹ , R ² and R ³ independently of the others is an optionally substituted, for example hydroxy- substituted, C ₁ -C ₃₀ hydrocarbon chain can be used. Amine oxides used with particular preference are those in which R ^{1 is} C ₁₂ -C ₁₈ alkyl and R ² and R ^{3 are} each independently C ₁ -C ₄ alkyl, in particular C ₁₂ -C ₁₈ alkyldimethylamine oxides. Exemplary representatives of suitable amine oxides are N-cocoalkyl-N, N-dimethylamine oxide, N-tallowalkyl-N, N-dihydroxyethylamine oxide, myristyl / cetyldimethylamine oxide or lauryldimethylamine oxide.

Suitable alkyl (poly) glycosides are, for example, those of the formula R ¹ O- [G] _p , in which R ^{1 is} a linear or branched alkyl with 12 to 16 carbon atoms, G is a sugar residue with 5 or 6 carbon atoms, in particular glucose, and the index p is 1 to 10.

Particularly preferred microemulsions according to the invention contain a surfactant system which, in addition to the at least one nonionic surfactant, also contains at least one anionic surfactant. It has been found that this surfactant combination can further increase the amount of said thickener stably incorporated into the microemulsion.

The term "anionic surfactant", as used herein, includes all surfactants with negatively charged functional groups, in particular sulfate, sulfonate and carboxylate groups and includes, for example, alkyl sulfates, olefin sulfonates, alkane sulfonates, alkyl ether sulfates, alkylbenzenesulfonates.

• jedes R³ unabhängig für H, CH₃ oder CH₂CH₃, insbesondere H, steht;
• jedes n unabhängig für 0 oder eine ganze Zahl von 1 bis 30, vorzugsweise 0 steht;
• X für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations steht, bevorzugt sind dabei die Alkalimetallionen und darunter Na⁺ oder K⁺, wobei Na⁺ äußerst bevorzugt ist, sowie NH₄ ⁺, ½ Zn²⁺,½ Mg²⁺,½ Ca²⁺,½ Mn²⁺, und deren Mischungen.

In various embodiments of the invention, the anionic surfactants used are in particular dialkyl sulfosuccinates and their salts, preferably alkali metal and ammonium salts, particularly preferably sodium and ammonium salts, and also derivatives thereof containing polyalkylene oxide units. The alkyl radicals can each independently be linear or branched and contain 6 to 22, preferably 6-12, carbon atoms. Preferred alkyl radicals are independently selected from 1-hexyl, 3,5,5-trimethyl-1-hexyl, isooctyl, such as, for example, 2-ethyl-1-hexyl, 6-methyl-1-heptyl, 2-methyl-1-heptyl, 2-propyl-1-pentyl, 2,4,4-trimethyl-1-pentyl, 1-ethyl-2-methyl-1-pentyl and 1,4-dimethyl-1-hexyl. Such surfactants include, for example, those of the formula

R ¹ - (OCHR ³ -CH ₂ ) _n -OC (O) -CH (SO ₃ X) -CH ₂ -C (O) -O- (CH ₂ -CHR ³ O) _n -R ²

where R ¹ and R ² independently represent linear or branched alkyl radicals having 6 to 22 carbon atoms, in particular 6 to 12 carbon atoms, which are preferably selected from 1-hexyl, 3,5,5-trimethyl-1-hexyl, isooctyl, such as 2-ethyl-1-hexyl, 6-methyl-1-heptyl, 2-methyl-1-heptyl, 2-propyl-1-pentyl, 2,4,4-trimethyl-1-pentyl, 1-ethyl-2-methyl-1-pentyl and 1,4-dimethyl-1-hexyl;

• each R ^{3 is} independently H, CH ₃ or CH ₂ CH ₃ , especially H;
• each n is independently 0 or an integer from 1 to 30, preferably 0;
• X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred, and NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

Of the surfactants mentioned, those in which R ¹ and R ^{2 are} identical and are selected from branched alkyl radicals, including but not limited to 3,5,5-trimethyl-1-hexyl, isooctyl, such as 2-ethyl- 1-hexyl, 6-methyl-1-heptyl, 2-methyl-1-heptyl, 2-propyl-1-pentyl, 2,4,4-trimethyl-1-pentyl, 1-ethyl-2-methyl-1- Pentyl and 1,4-dimethyl-1-hexyl, in particular isooctyl such as, for example, 2-ethyl-1-hexyl, 6-methyl-1-heptyl and 2-methyl-1-heptyl. In such surfactants, R ^{3 is} preferably H and n is 0. Sodium bis (isooctyl) sulfosuccinates, such as, for example, sodium bis (2-ethyl-1-hexyl) sulfosuccinate, sodium bis (6-methyl-1-heptyl) sulfosuccinate and sodium bis are particularly preferred (2-methyl-1-heptyl) sulfosuccinate. Alternatively, the corresponding acids can also be used.

wobei die Reste R¹ und R² jeweils unabhängig voneinander linear oder verzweigt sind und 6 bis 22 Kohlenstoffatome, vorzugsweise 6 bis 12 Kohlenstoffatome, enthalten und besonders bevorzugt ausgewählt werden aus 1-Hexyl, 3,5,5-Trimethyl-1-Hexyl, 2-Ethyl-1-Hexyl, 6-Methyl-1-Heptyl, 2-Methyl-1-Heptyl, 2-Propyl-1-Pentyl, 2,4,4-Trimethyl-1-pentyl, 1-Ethyl-2-Methyl-1-Pentyl und 1,4-Dimethyl-1-hexyl, und
1/n Mⁿ⁺ ein Äquivalent eines n-wertigen Kations ist.Dialkyl sulfosuccinates of the formula (A-1) or combinations thereof are very particularly preferred,

where the radicals R ¹ and R ^{2 are} each independently linear or branched and contain 6 to 22 carbon atoms, preferably 6 to 12 carbon atoms, and are particularly preferably selected from 1-hexyl, 3,5,5-trimethyl-1-hexyl, 2-ethyl-1-hexyl, 6-methyl-1-heptyl, 2-methyl-1-heptyl, 2-propyl-1-pentyl, 2,4,4-trimethyl-1-pentyl, 1-ethyl-2- Methyl-1-pentyl and 1,4-dimethyl-1-hexyl, and
1 / n M ^{n + is} an equivalent of an n-valent cation.

Additionally or alternatively, the surfactant system can contain further anionic surfactants. In various embodiments, these are selected from alkyl benzene sulfonates, olefin sulfonates, alkane sulfonates, alkyl ester sulfonates, alk (en) yl sulfates, alkyl ether sulfates, N-acyl taurides, polyether sulfonates and mixtures of two or more of these anionic surfactants. Further suitable anionic surfactants are soaps, ie salts of fatty acids, in particular the Na or K salts of fatty acids. Saturated and unsaturated are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.

Surfactants of the sulfonate type are preferably alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C _12-18 monoolefins with terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and then alkaline or acidic Hydrolysis of the sulfonation products obtained, into consideration. Also suitable are C _12-18 alkane sulfonates and the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids and taurides and polyether sulfonates.

Alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula

R-SO ₃ ^- X ⁺

In this formula, R stands for a linear or branched, unsubstituted alkylaryl radical. X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X ⁺ can be selected from NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof. "Alkylaryl" as used herein refers to organic radicals consisting of an alkyl radical and an aromatic radical. Typical examples of such groups include, but are not limited to, alkylbenzene groups such as benzyl, butylbenzene groups, nonylbenzene groups, decylbenzene groups, undecylbenzene groups, dodecylbenzene groups, tridecylbenzene groups, and the like.

in der R' und R" zusammen 8 bis 19, vorzugsweise 8 bis 15 und insbesondere 8 bis 12 C-Atome enthalten, dargestellt. Ein ganz besonders bevorzugter Vertreter ist Natriumdodecylbenzylsulfonat.In various embodiments, such surfactants are selected from linear or branched alkylbenzenesulfonates of the formula

in which R 'and R "together contain 8 to 19, preferably 8 to 15 and in particular 8 to 12 carbon atoms. A very particularly preferred representative is sodium dodecylbenzyl sulfonate.

Further usable anionic surfactants are the alkyl ester sulfonates, in particular those of the formula

R ¹ CH (SO ₃ ^- X ⁺⁾ -C (O) -OR ²

In this formula, R ¹ stands for a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical. Preferred radicals R ¹ are selected from nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl radicals and mixtures thereof, the representatives with an odd number of carbon atoms are preferred. Particularly preferred radicals R ¹ —CH are derived from C ₁₂ -C ₁₈ fatty acids, for example from lauric, myristyl, cetyl or stearic acid. R ² represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical. Preferred radicals R ² are C _1-6 alkyl radicals, in particular methyl (= methyl ester sulfonate). X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X ⁺ can be selected from NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

The secondary alkane sulfonates are also suitable as anionic surfactants. These have for example the formula

R ¹ CH (SO ₃ ^- X ⁺ ) R ²

where each R ¹ and R ^{2 is} independently a linear or branched alkyl having 1 to 20 carbon atoms and with the carbon atom to which they are attached to form a linear or branched alkyl, preferably having 10 to 30 carbon atoms, preferably 10 to 20 carbon atoms and X ^{+ is} selected from the group Na ⁺ , K ⁺ , NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ and mixtures thereof, preferably Na ⁺ .

In various preferred embodiments, the at least one secondary alkanesulfonate has the formula below

H ₃ C- (CH _{2) n} -CH (SO ₃ -X ⁺⁾ - (CH ₂₎ m CH ₃

where m and n are independently an integer between 0 and 20. Preferably m + n is an integer between 7 and 17, preferably 10 to 14 and X ⁺ is selected from the group Na ⁺ , K ⁺ , NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ and mixtures thereof, preferably Na ⁺ . In a particularly preferred embodiment, the at least one secondary alkanesulfonate is secondary C _14-17 sodium alkanesulfonate. Such a secondary C _14-17 sodium alkanesulfonate is sold, for example, by the Clariant company under the trade name "Hostapur SAS60".

Suitable taurides are those of the general formula

RC (O) -N (CH ₃ ) -CH ₂ CH ₂ -SO ₃ ^- X ⁺

where R is a linear or branched, preferably odd-numbered, alkyl radical having 6 to 30, preferably 7 to 17 carbon atoms.

Further suitable anionic surfactants are those in EP2203419 A1 described polyethersulfonates of the formula

R ¹ -O- (CH ₂ -CHR ₂ O) _n CH ₂ -C (O) -CH ₂ -SO ₃ -X ⁺

where R ^{1 stands} for a straight-chain, branched, saturated or unsaturated aliphatic and / or aromatic hydrocarbon ^{radical with 6 to 30 carbon atoms, R 2} independently of one another for each of the k alkoxy units for hydrogen or a straight-chain, branched, aliphatic or aromatic hydrocarbon radical with 1 to 10 carbon atoms , n for a number from 0 to 35, and X ⁺ for H ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ and mixtures thereof, preferably Na ⁺ .

Particularly preferred are alkyl ether sulfates with the formula (A-3)

R ¹ -O- (AO) _n -SO ₃ ^- X ⁺ (A-3)

suitable. In formula (A-3), R ^{1 represents} a linear or branched, substituted or unsubstituted (C ₁₀ -C ₂₀ ) -alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols.

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2 ). Der angegebenen Ethoxylierungsgrad stellt einen statistischen Mittelwert dar, der für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein kann. Die angegebenen Alkoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoxylate/Ethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE).According to formula (A-3), AO represents an ethylene oxide (EO) or propylene oxide (PO) grouping, preferably an ethylene oxide group. According to formula (A-3), the index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Very particularly preferably n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. According to formula (A-3), X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X + can be selected from NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof Particularly preferred detergents contain an alkyl ether sulfate selected from fatty alcohol ether sulfates of the formula

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-C _12-14 fatty alcohol ether sulfates with 2 EO (k = 11-13, n = 2). The stated degree of ethoxylation represents a statistical mean value which, for a specific product, can be an integer or a fraction. The stated degrees of alkoxylation represent statistical mean values which, for a specific product, can be an integer or a fraction. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

The alk (en) yl sulfates are the salts of the sulfuric acid half esters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half esters secondary alcohols of these chain lengths are preferred. From the point of view of washing technology, the C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and also C ₁₄ -C ₁₅ -alkyl sulfates are preferred. 2,3-Alkyl sulfates are also suitable anionic surfactants. Accordingly, the alkyl sulfates of the formula can generally be used

R ^1- O-SO ₃ ^- X ⁺ (A-4).

In this formula (A-4), R ^{1 represents} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ² are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₃ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols. X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X ⁺ can be selected from NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholsulfate (k = 11-13).In various embodiments, these surfactants are selected from fatty alcohol sulfates of the formula

with k = 11 to 19. Very particularly preferred representatives are Na-C _12-14 fatty alcohol sulfates (k = 11-13).

The aforementioned anionic surfactants, including the fatty acid soaps, can also be in the form of acids, but are preferably in the form of their sodium, potassium or magnesium or ammonium salts. The sodium salts and / or ammonium salts are particularly preferred. Amines which can be used for neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine or a mixture thereof, monoethanolamine being preferred.

Very particularly preferred microemulsions are characterized in that the at least one anionic surfactant is selected from C ₉ -C ₁₅ -alkylbenzenesulfonate, C ₁₀ -C ₂₀ -alkyl ether sulfate, (C ₆ -C ₂₂ ) -dialkyl sulfosuccinates or mixtures thereof. In turn, these anionic surfactants are very particularly preferably selected from surfactants of the formulas described above, in particular formulas (A-1), (A-2), (A-3) and (A-4).

In preferred embodiments of the invention, the surfactant system comprises at least one alkyl ether as the nonionic surfactant, preferably a C _8-20 fatty alcohol alkoxylate with 1 to 10 EO and 0 to 10 PO and at least one dialkyl sulfosuccinate (as described above) as the anionic surfactant. The weight ratio of anionic to nonionic surfactant can be 100: 1 to 1: 100, preferably 25: 1 to 1:25, in certain particularly preferred embodiments 1: 2 to 1:10.

1. a) eine Gesamtmenge von 5 bis 20 Gew.-% Wasser als flüssige Phase,
2. b) eine Gesamtmenge von 40 bis 90 Gew.-% mindestens eines nicht-polymeren, organischen Verdickungsmittels mit einem Molekulargewicht im Bereich von 100 g/mol bis 1500 g/mol als emulgierte Phase und
3. c) ein Tensidsystem, enthaltend jeweils bezogen auf das Gewicht der Mikroemulsion jeweils eine Gesamtmenge von
   • c1) 5 bis 15 Gew.-% mindestens eines ein C_8-20 Fettalkoholalkoxylat mit 1 bis 10 EO und 0 bis 10 PO als nichtionisches Tensid und
   • c2) 10 bis 15 Gew.-% mindestens eines Dialkylsulfosuccinat (wie oben beschrieben) als anionisches Tensid,
   • wobei das Gewichtsverhältnis von c1) und c2) in einem Gewichtsverhältnisbereich von 2 zu 1 bis 1 zu 2 liegt.

Microemulsions according to the invention, each based on the total weight of the microemulsion, are very particularly preferred

1. a) a total amount of 5 to 20% by weight of water as the liquid phase,
2. b) a total amount of 40 to 90% by weight of at least one non-polymeric, organic thickener with a molecular weight in the range from 100 g / mol to 1500 g / mol as the emulsified phase and
3. c) a surfactant system, each containing, based on the weight of the microemulsion, in each case a total amount of
   • c1) 5 to 15% by weight of at least one C _8-20 fatty alcohol alkoxylate with 1 to 10 EO and 0 to 10 PO as a nonionic surfactant and
   • c2) 10 to 15% by weight of at least one dialkyl sulfosuccinate (as described above) as an anionic surfactant,
   • wherein the weight ratio of c1) and c2) is in a weight ratio range of 2: 1 to 1: 2.

In preferred embodiments, the surfactant system comprises an alkyl ether as the nonionic surfactant, preferably a C _8-20 fatty alcohol alkoxylate with 1 to 10 EO and 0 to 10 PO and at least one C ₈ -C ₁₂ -alkylbenzenesulfonate as the anionic surfactant.

1. a) eine Gesamtmenge von 5 bis 50 Gew.-%, insbesondere 5 bis 30 Gew.-%, Wasser als flüssige Phase,
2. b) eine Gesamtmenge von 2,5 bis 90 Gew.-%, insbesondere 20 bis 90 Gew.-% mindestens eines nicht-polymeren, organischen Verdickungsmittels mit einem Molekulargewicht im Bereich von 100 g/mol bis 1500 g/mol als emulgierte Phase und
3. c) ein Tensidsystem, enthaltend jeweils bezogen auf das Gewicht der Mikroemulsion jeweils eine Gesamtmenge von
   • c1) 3 bis 40 Gew.-% mindestens eines ein C_8-20 Fettalkoholalkoxylat mit 1 bis 10 EO und 0 bis 10 PO als nichtionisches Tensid und
   • c2) 10 bis 40 Gew.-% mindestens eines C₈-C₁₂-Alkylbenzolsulfonat als anionisches Tensid, wobei das Gewichtsverhältnis von c1) und c2) in einem Gewichtsverhältnisbereich von 15 zu 1 bis 1 zu 15 liegt. sind nicht erfindungsgemäss.

Microemulsions in the form of an O / W emulsion, each based on the total weight of the microemulsion

1. a) a total amount of 5 to 50% by weight, in particular 5 to 30% by weight, of water as the liquid phase,
2. b) a total amount of 2.5 to 90% by weight, in particular 20 to 90% by weight, of at least one non-polymeric, organic thickener with a molecular weight in the range from 100 g / mol to 1500 g / mol as the emulsified phase and
3. c) a surfactant system, each containing, based on the weight of the microemulsion, in each case a total amount of
   • c1) 3 to 40% by weight of at least one C _8-20 fatty alcohol alkoxylate with 1 to 10 EO and 0 to 10 PO as a nonionic surfactant and
   • c2) 10 to 40% by weight of at least one C ₈ -C ₁₂ -alkylbenzenesulfonate as anionic surfactant, the weight ratio of c1) and c2) being in a weight ratio range of 15: 1 to 1: 15. are not according to the invention.

The microemulsion according to the invention necessarily contains at least one liquid phase. This liquid phase is different from the surfactant system and the said thickener. In a preferred O / W emulsion, the at least one liquid phase is water.

The liquid phase is contained in the microemulsion according to the invention preferably in a total amount between 0 and 50% by weight, in particular from 10 to 40% by weight.

The microemulsions according to the invention are easy to dose. They have a preferred viscosity of 10 ^-1 to 10 ⁴ mPa * s.

1. i) bezogen auf das Gewicht der Mikroemulsion eine Gesamtmenge von 10 Gew.-% bis 99,0 Gew.-% mindestens eines nicht-polymeren, organischen Verdickungsmittels mit einem Molekulargewicht von 100 g/mol bis 1500 g/mol als erste flüssige Phase mit mindestens einer Flüssigkeit als zweite flüssige Phase, mindestens einem Tensid C1 und mindestens einem nichtionischen Tensid C2 gemischt werden, so dass eine trübe Mischung entsteht, und
2. ii) das Gemisch auf eine Temperatur T1 gebracht und weiter durchgemengt wird,

mit der Maßgabe, dass die Temperatur T1 wenigstens so hoch wie der Schmelzpunkt mindestens eines besagten niedermolekularen Verdickungsmittels aus Schritt i) ist und eine Mikroemulsion erhalten wird.A second subject matter of the invention is a method for producing the microemulsions of the first subject matter of the invention. Said microemulsions are obtained by a process for the preparation of a microemulsion existing at a temperature T1, wherein

1. i) based on the weight of the microemulsion, a total amount of 10% by weight to 99.0% by weight of at least one non-polymeric, organic thickener with a molecular weight of 100 g / mol to 1500 g / mol as the first liquid phase at least one liquid as the second liquid phase, at least one surfactant C1 and at least one nonionic surfactant C2 are mixed, so that a cloudy mixture is formed, and
2. ii) the mixture is brought to a temperature T1 and mixed further,

with the proviso that the temperature T1 is at least as high as the melting point of at least one said low molecular weight thickener from step i) and a microemulsion is obtained.

For this purpose, at least one first surfactant C1, whereby this at least one first surfactant can also be a mixture of several surfactants, is presented in a concentration that is below the fishtail point, and a second amphiphile / surfactant C2 at a constant temperature and constant water: oil ratio (which is different from the at least one surfactant C1) added. The surfactant C1 is preferably at least one nonionic surfactant and / or at least one anionic surfactant and the surfactant C2 is preferably at least one nonionic surfactant Subject matter of the invention applies mutatis mutandis to the second subject matter of the invention.

A method preferred according to the invention is characterized in that the at least one surfactant C2 is only added after step ii).

The temperature T1 is at least as high as the melting point of at least one said low molecular weight thickener from step i). The aim is to transfer the said thickeners completely into a liquid phase. It is either possible, in the case of a thickening agent mixture, for the solid thickening agents to dissolve in the at least one liquid thickening agent. On the other hand, it is also possible, in the case of a mixture of thickeners, for the temperature T1 to be selected such that it assumes at least the value of the highest melting point of the thickeners used. The temperature T1 of the process according to the invention is preferably in a temperature range from 20 to 100 ° C, more preferably between 30 ° C and 100 ° C, preferably from 40 to 98 ° C, particularly preferably between 40 ° C and 95 ° C, very particularly preferred from 70 ° C to 90 ° C, more preferably from 75 to 95 ° C.

• eine Gesamtmenge von 5 bis 80 Gew.-% mindestens eines Tensids enthält und
• eine Fließgrenze, insbesondere von 0,001 bis 6 Pa, besonders bevorzugt von 0,1 bis 3 Pa, aufweist.

A third subject of the invention is a liquid surfactant composition, in particular a liquid detergent, which, based on the total weight of the liquid surfactant composition, has a total amount of 0.001% by weight to 5% by weight of at least one microemulsion of the first subject of the invention with a composition containing water and at least one surfactant is obtained, with the provisos that the liquid surfactant composition in each case

• contains a total amount of 5 to 80% by weight of at least one surfactant and
• has a flow limit, in particular from 0.001 to 6 Pa, particularly preferably from 0.1 to 3 Pa.

The total amount of said non-polymeric, organic thickener introduced by the microemulsion according to the invention, based on the total weight of the liquid tenis composition, is preferably 0.001% by weight to 5.0% by weight, particularly preferably 0.01% by weight to 3, 0% by weight.

To develop a cleaning or washing performance, the liquid surfactant compositions according to the invention contain at least one surfactant, particularly preferably a mixture of several surfactants from different classes of substances. All surfactants mentioned in the first subject of the invention are suitable.

It is preferred for the invention if the total amount of surfactant is 5.0 to 70% by weight, preferably 8.0 to 60.0% by weight, more preferably from 10.0 to 50.0% by weight , particularly preferably from 15.0 to 45.0% by weight, based in each case on the total weight of the liquid surfactant composition.

According to the invention, at least one anionic surfactant is preferably used as the surfactant.

All anionic surface-active substances are suitable as anionic surfactants in the liquid surfactant compositions according to the invention. These are characterized by a water-solubilizing, anionic group such. B. a carboxylate, sulfate, sulfonate or phosphate group and a lipophilic alkyl group with about 8 to 30 carbon atoms. In addition, the molecule can contain glycol or polyglycol ether groups, ester, ether and amide groups as well as hydroxyl groups. Suitable anionic surfactants are preferably in the form of the sodium, potassium and ammonium as well as the mono-, di- and trialkanolammonium salts with 2 to 4 carbon atoms in the alkanol group.

Preferred liquid surfactant compositions according to the invention contain, based on the total weight of the composition, anionic surfactant in a total amount of from 5.0 to 35.0% by weight, preferably from 8.0 to 30.0% by weight, particularly preferably from 10.0 to 25.0 wt%.

Preferred anionic surfactants in the liquid surfactant compositions according to the invention are alkyl sulfates, alkyl polyglycol ether sulfates and alkyl benzene sulfonates, each with 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule.

Preferred liquid surfactant compositions according to the invention used according to the invention contain at least one surfactant of the formula (A-3)

R ¹ -O- (AO) _n -SO ₃ ^- X ⁺ . (A-3)

In this formula, R ¹ stands for a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols.

AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably for an ethylene oxide group. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. Very particularly preferably n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X + can be selected from NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2 in Formel A-3a).In summary, particularly preferred liquid surfactant compositions according to the invention contain at least one anionic surfactant selected from fatty alcohol ether sulfates of the formula A-3a

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-C _12-14 fatty alcohol ether sulfates with 2 EO (k = 11-13, n = 2 in the formula A-3a).

Preferred liquid surfactant compositions according to the invention contain, based on the total amount of the composition, 1.0 to 15% by weight, preferably 2.5 to 12.5% by weight, more preferably 5.0 to 10.0% by weight of fatty alcohol ether sulfate (e ) (in each case in particular of the formula A-3a).

Further preferred liquid surfactant compositions according to the invention additionally or alternatively (in particular additionally) contain at least one surfactant of the formula (A-5)

R ³ -A-SO ₃ ^- 1 / n Y ^{n +} (A-5)

In this formula, R ³ stands for a linear or branched, substituted or unsubstituted alkyl radical, a linear or branched, substituted or unsubstituted aryl radical or a linear or branched, substituted or unsubstituted alkylaryl radical and the grouping -A- stands for -O- or a chemical bond . In other words, the above formula can be used to describe sulfate (A = O) or sulfonate (A = chemical bond) surfactants. Depending on the choice of group A, certain radicals R ^{3 are} preferred. In the sulfate surfactants (A = O), R ³ preferably represents a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C- Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols. 1 / n Y ^{n +} represents the n-th part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations Y ⁺ can be selected from NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholsulfate (k = 11-13 in Formel A-5a).Such surfactants are selected from fatty alcohol sulfates of the formula A-5a

with k = 11 to 19. Very particularly preferred representatives are Na-C _12-14 fatty alcohol sulfates (k = 11-13 in formula A-5a).

Further preferred liquid surfactant compositions according to the invention contain, based on the total amount of the compositions, 1.0 to 25.0% by weight, preferably 2.5 to 20.5% by weight, more preferably 5.0 to 20.0% by weight Surfactant from the group comprising C _9-13 -alkylbenzenesulfonates, (C ₈ -C ₂₂ ) -olefin sulfonates, C _12-18 -alkanesulfonates, (C ₈ -C ₂₂ ) -ester sulfonates, (Cs-C ₂₂ ) -alk (en) yl sulfates, and mixtures thereof (in particular the group of the C _9-13 -alkylbenzenesulfonates, preferably the group according to formula (A-2)).

In the sulfonate surfactants (A = chemical bond), which are preferred over the sulfate surfactants of the above formula, R ³ preferably represents a linear or branched unsubstituted alkylaryl radical. Here, too, X stands for a monovalent cation or the nth part of an n-valent cation, preferred are the alkali metal ions, including Na ⁺ or K ⁺ , Na ^{+ being} extremely preferred. Further cations X + can be selected from NH ₄ ⁺ , ½ Zn ²⁺ , ½ Mg ²⁺ , ½ Ca ²⁺ , ½ Mn ²⁺ , and mixtures thereof.

in der R' und R" zusammen 9 bis 19, vorzugsweise 11 bis 15 und insbesondere 11 bis 13 C-Atome enthalten. Ein ganz besonders bevorzugter Vertreter lässt sich durch die Formel A-2a beschreiben:

Such highly preferred surfactants are selected from linear or branched alkylbenzenesulfonates of the formula A-2

in which R 'and R "together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 carbon atoms. A very particularly preferred representative can be described by the formula A-2a:

It has proven to be advantageous for cold washing performance if the liquid surfactant compositions according to the invention additionally contain soap (s) as an anionic surfactant. Soaps are the water-soluble sodium or potassium salts of saturated and unsaturated fatty acids with 10 to 20 carbon atoms, the resin acids of rosin (yellow resin soaps) and naphthenic acids, which are used as solid or semi-solid mixtures mainly for washing and cleaning purposes. Sodium or potassium salts of saturated and unsaturated fatty acids with 10 to 20 carbon atoms, in particular with 12 to 18 carbon atoms, are preferred soaps according to the invention. Particularly preferred compositions are characterized in that they - based on their weight - 0.1 to 6% by weight, particularly preferably 0.2 to 4.5% by weight, very particularly preferably 0.3 to 4.1 Contain% by weight of soap (s).

• mindestens einem Fettalkoholethersulfat der Formel A-3a
  
  mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8 (besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2 in Formel A-3), und
• mindestens einem linearen oder verzweigten Alkylbenzolsulfonaten der Formel A-2
  
  in der R' und R" zusammen 9 bis 19, vorzugsweise 11 bis 15 und insbesondere 11 bis 13 C-Atome enthalten (insbesondere der obigen Formel (A-2a)),

To improve the solution to the technical problem, it is very particularly preferred according to the invention to use a combination of

• at least one fatty alcohol ether sulfate of the formula A-3a
  
  with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8 (particularly preferred representatives are Na-C _12-14 fatty alcohol ether sulfates with 2 EO (k = 11-13, n = 2 in formula A -3), and
• at least one linear or branched alkylbenzenesulfonate of the formula A-2
  
  in which R 'and R "together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 carbon atoms (in particular of the above formula (A-2a)),

to be used in the surfactant compositions of the invention. Preferred surfactant compositions of this embodiment are optionally characterized in that they contain one or more soaps (preferably - based on their weight - 0.1 to 6% by weight, particularly preferably 0.2 to 4.5% by weight, very particularly preferably 0.3 to 4.1% by weight of soap (s)).

In addition to or instead of the anionic surfactant (s), the liquid surfactant compositions according to the invention preferably contain at least one nonionic surfactant.

The surfactant compositions particularly preferably contain at least one nonionic surfactant from the group of (C ₈ -C ₂₂ ) fatty alcohol ethoxylates, since these surfactants give high-performance compositions even at low washing temperatures and, in the case of liquid preparations, have excellent cold stability.

R2

für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkyl-, Aryl- oder Alkylarylrest,

AO

für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung,

m

für ganze Zahlen von 1 bis 50 stehen.

Accordingly, particularly preferred liquid surfactant compositions additionally contain at least one nonionic surfactant of the formula

R ² -O- (AO) _m -H,

in the

R2

for a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical,

AO

for an ethylene oxide (EO) or propylene oxide (PO) group,

m

stand for whole numbers from 1 to 50.

In the above formula, R ^{2 represents} a linear or branched, substituted or unsubstituted alkyl, branched, substituted or unsubstituted aryl radical or branched, substituted or unsubstituted alkylaryl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R ² are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of carbon atoms being preferred. Particularly preferred radicals R ² are derived from C ₁₂ -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C ₁₀ -C ₂₀ oxo alcohols.

AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably for an ethylene oxide group. The index m stands for an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. m is very particularly preferably the numbers 2, 3, 4, 5, 6, 7 or 8.

mit k = 11 bis 19, m = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind C_12-18 Fettalkohole mit 7 EO (k = 11-17, m = 7 in Formel A-6).In summary, particularly preferred surfactants are selected from fatty alcohol ethoxylates of the formula A-6

with k = 11 to 19, m = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are C _12-18 fatty alcohols with 7 EO (k = 11-17, m = 7 in formula A- 6).

Particularly preferred compositions contain nonionic surfactants in certain amounts. Extremely preferred liquid surfactant compositions according to the invention are characterized in that the total amount of nonionic surfactants based on the weight of the compositions is 1.0 to 25% by weight, preferably 2.5 to 20.0% by weight, more preferably 5.0 to 18.0 wt%.

More preferred compositions contain, based on the total amount of the compositions, 1.0 to 25% by weight, preferably 2.5 to 20.0% by weight, more preferably 5.0 to 18.0% by weight of fatty alcohol ethoxylate (s) (especially of the formula (A-6)).

• anionisches Tensid in einer Gesamtmenge von 1,0 bis 35,0 Gew.-%, bevorzugt von 5,0 bis 30,0 Gew.-%, besonders bevorzugt von 10,0 bis 25,0 Gew.-%, und
• nichtionisches Tensid in einer Gesamtmenge von 1,0 bis 25 Gew.-%, vorzugsweise 2,5 bis 20,0 Gew.-%, weiter bevorzugt 5,0 bis 18,0 Gew.-%.

Preferred liquid surfactant compositions according to the invention contain based on the total weight of the composition

• anionic surfactant in a total amount of from 1.0 to 35.0% by weight, preferably from 5.0 to 30.0% by weight, particularly preferably from 10.0 to 25.0% by weight, and
• nonionic surfactant in a total amount of 1.0 to 25% by weight, preferably 2.5 to 20.0% by weight, more preferably 5.0 to 18.0% by weight.

Here it is again preferred to use the preferred surfactants (most preferably in the amounts marked as preferred). In this case, the amount of the special anionic and nonionic surfactants is to be selected so that the total amount defined above of anionic surfactant and the previously defined total amount of nonionic surfactant is complied with.

1. i) mindestens ein anionisches Tensid der Formel R¹-O-(AO)_n-SO₃ ^- X⁺, und
2. ii) mindestens ein anionisches Tensid der Formel A-2
   
   und
3. iii) mindestens ein nichtionisches Tensid der Formel R²-O-(AO)_m-H, enthalten, in denen

   R1

   für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkyl-, Aryl- oder Alkylarylrest,

   R' und R"

   zusammen 9 bis 19, vorzugsweise 11 bis 15 und insbesondere 11 bis 13 C-Atome enthalten,

   AO

   unabhängig voneinander für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung,

   n, m

   unabhängig voneinander für ganze Zahlen von 1 bis 50,

   X

   für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations stehen.

According to a particularly preferred embodiment, those compositions are preferred which

1. i) at least one anionic surfactant of the formula R ¹ -O- (AO) _n -SO ₃ ^- X ⁺ , and
2. ii) at least one anionic surfactant of the formula A-2
   
   and
3. iii) contain at least one nonionic surfactant of the formula R ² -O- (AO) _m -H, in which

   R1

   for a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical,

   R 'and R "

   together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 carbon atoms,

   AO

   independently of one another for an ethylene oxide (EO) or propylene oxide (PO) group,

   n, m

   independently of each other for whole numbers from 1 to 50,

   X

   stand for a monovalent cation or the n-th part of an n-valent cation.

The surfactants i) and ii) were described above as preferred surfactants a) with the formulas (A-3) and (A-2a), the surfactant iii) as the preferred surfactant with the formula (A-6). Preferred compositions of this embodiment are in turn characterized in that they additionally contain at least one soap.

1. i) in einer Gesamtmenge von 1,0 bis 15 Gew.-%, vorzugsweise 2,5 bis 12,5 Gew.-%, weiter bevorzugt 5,0 bis 10,0 Gew.-% mindestens ein anionisches Tensid der Formel R¹-O-(AO)_n-SO₃ ^- X⁺, und
2. ii) in einer Gesamtmenge von 1,0 bis 25 Gew.-%, vorzugsweise 2,5 bis 20,5 Gew.-%, weiter bevorzugt 5,0 bis 20,0 Gew.-% mindestens ein anionisches Tensid der Formel A-2
   
   und
3. iii) in einer Gesamtmenge von 1,0 bis 25 Gew.-%, vorzugsweise 2,5 bis 20,0 Gew.-%, weiter bevorzugt 5,0 bis 18,0 Gew.-% mindestens ein nichtionisches Tensid der Formel R²-O-(AO)_m-H,

enthalten, in denen

R1

für einen linearen oder verzweigten, substituierten oder unsubstituierten Alkyl-, Aryl- oder Alkylarylrest,

R' und R"

zusammen 9 bis 19, vorzugsweise 11 bis 15 und insbesondere 11 bis 13 C-Atome enthalten,

AO

unabhängig voneinander für eine Ethylenoxid- (EO) oder Propylenoxid- (PO) Gruppierung,

n, m

unabhängig voneinander für ganze Zahlen von 1 bis 50,

X

für ein einwertiges Kation oder den n-ten Teil eines n-wertigen Kations stehen,

According to a very particularly preferred embodiment, those compositions are preferred that are based on the weight of the composition

1. i) in a total amount of 1.0 to 15% by weight, preferably 2.5 to 12.5% by weight, more preferably 5.0 to 10.0% by weight, of at least one anionic surfactant of the formula R ¹ -O- (AO) _n -SO ₃ ^- X ⁺ , and
2. ii) in a total amount of 1.0 to 25% by weight, preferably 2.5 to 20.5% by weight, more preferably 5.0 to 20.0% by weight, at least one anionic surfactant of the formula A- 2
   
   and
3. iii) in a total amount of 1.0 to 25% by weight, preferably 2.5 to 20.0% by weight, more preferably 5.0 to 18.0% by weight, at least one nonionic surfactant of the formula R ² -O- (AO) _m -H,

included in which

R1

for a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical,

R 'and R "

together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 carbon atoms,

AO

independently of one another for an ethylene oxide (EO) or propylene oxide (PO) group,

n, m

independently of each other for whole numbers from 1 to 50,

X

stand for a monovalent cation or the nth part of an n-valent cation,

Preferred surfactant compositions of this embodiment are in turn characterized in that they contain 0.1 to 6% by weight, particularly preferably 0.2 to 4.5% by weight, very particularly preferably 0.3 to 4% by weight, based on their weight Contain 1% by weight of soap (s).

The liquid surfactant composition according to the invention can contain water as the solvent. Compositions preferred according to the invention contain water in an amount between 1 to 55% by weight, in particular from 2 to 50% by weight, based in each case on the total weight of the composition.

It is preferred that the liquid surfactant composition is more than 5% by weight, preferably more than 15% by weight and particularly preferably more than 25% by weight, very particularly preferably more than 40% by weight, in each case based on the Total amount of detergent that contains water. It is again particularly preferred if the detergent contains less than 55% by weight, preferably less than 50% by weight and particularly preferably less than 45% by weight, based in each case on the total amount of detergent, of water.

Liquid surfactant compositions are preferably characterized in that the weight ratio of the amount of surfactant in the microemulsion to the total amount of surfactant in the liquid surfactant composition is in a range of a maximum of 1 to 2, in particular of a maximum of 1:30, particularly preferably a maximum of 1 to 100.

Very particularly preferred liquid surfactant compositions of the present invention additionally contain solid particles (hereinafter also referred to as particles) suspended in the liquid surfactant composition. Such suspended solid particles are to be understood as solids which do not dissolve at 20 ° C. in the liquid phase of the surfactant composition according to the invention and are present as a separate phase.

The particles are preferably selected from polymers, pearlescent pigments, microcapsules, speckles or mixtures thereof.

Microcapsules in the context of the present invention include any type of capsule known to the person skilled in the art, but in particular core-shell capsules and matrix capsules. Matrix capsules are porous molded bodies that have a structure similar to a sponge. Core-shell capsules are shaped bodies that have a core and a shell. Suitable microcapsules are those capsules which have an average diameter X _50.3 (volume average) of 0.1 to 200 μm, preferably 1 to 100 μm, more preferably 5 to 80 μm, particularly preferably 10 to 50 μm and in particular 15 to 40 µm. The mean particle size diameter X _50.3 is determined by sieving or by means of a Camsizer particle size analyzer from Retsch.

The microcapsules of the invention preferably contain at least one active ingredient, preferably at least one fragrance. These preferred microcapsules are perfume microcapsules.

In a preferred embodiment of the invention, the microcapsules have a semipermeable capsule wall (shell).

A semipermeable capsule wall within the meaning of the present invention is a capsule wall that is semi-permeable, i.e. continuously releases small amounts of the capsule core over time without the capsule being damaged or opened, e.g. by friction. Such capsules continuously release small amounts of the active ingredient in the capsule, e.g. perfume, over a longer period of time.

In a further preferred embodiment of the invention, the microcapsules have an impermeable shell. An impermeable shell in the sense of the present invention is a capsule wall which is essentially impermeable, that is to say only releases the capsule core when the capsule is damaged or opened. Such capsules contain significant amounts of the at least one fragrance in the capsule core, so that a very intense fragrance is provided when the capsule is damaged or opened. The scent intensities achieved in this way are usually so high that Smaller amounts of the microcapsules can be used in order to achieve the same fragrance intensity as with conventional microcapsules.

In a preferred embodiment of the invention, the surfactant composition according to the invention contains both microcapsules with a semipermeable shell and also microcapsules with an impermeable shell. By using both types of capsules, a significantly improved fragrance intensity can be provided over the entire laundry cycle.

In a further preferred embodiment of the invention, the composition according to the invention can also contain two or more different types of microcapsules with a semipermeable or impermeable shell.

The materials used for the shell of the microcapsules are usually high molecular weight compounds such as protein compounds such as gelatin, albumin, casein and others, cellulose derivatives such as methyl cellulose, ethyl cellulose, cellulose acetate, cellulose nitrate, carboxymethyl cellulose and others and above all also synthetic polymers such as polyamides, polyethylene glycols, polyurethanes, epoxy resins and others. The wall material, ie the shell, melamine-formaldehyde polymer, melamine-urea polymer, melamine-urea-formaldehyde polymer, polyacrylate polymer or polyacrylate copolymer is preferably used. Capsules according to the invention are, for example, but not exclusively, in US 2003/0125222 A1 , DE 10 2008 051 799 A1 or WO 01/49817 described.

Preferred melamine-formaldehyde microcapsules are produced by placing melamine-formaldehyde precondensates and / or their C ₁ -C ₄ -alkyl ethers in water, in which the at least one odor modulator compound and optionally other ingredients, such as at least one fragrance, are in Condensed in the presence of a protective colloid. Suitable protective colloids are, for example, cellulose derivatives, such as hydroxyethyl cellulose, carboxymethyl cellulose and methyl cellulose, polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone, polyvinyl alcohols, partially hydrolyzed polyvinyl acetates, gelatin, gum arabic, xanthan gum acid, alginates, polyacrylic acid, polyacrylic acid, pectinic acid, alginates, polyacrylates, pectins, alginates, polyacrylates, polyacrylic acid, copolymers, polyacrylic acid, pectinic acid, alginates, polyacrylic acid, pectinic acid copolymers and methacrylic acid, water-soluble polymers containing sulfonic acid groups and containing sulfoethyl acrylate, sulfoethyl methacrylate or sulfopropyl methacrylate, and polymers of N- (sulfoethyl) maleimide, 2-acrylamido-2-alkylsulfonic acids, styrenesulfonic acids and formaldehyde and condensates of phenolsulfonic acids and formaldehyde.

It is preferred to completely or partially coat the surface of the microcapsules used according to the invention with at least one cationic polymer. Correspondingly, at least one cationic polymer from Polyquaternium-1, Polyquaternium-2, Polyquaternium-4, Polyquaternium-5, Polyquaternium-6, is suitable as a cationic polymer for coating the microcapsules, Polyquaternium-7, Polyquaternium-8, Polyquaternium-9, Polyquaternium-10, Polyquaternium-11, Polyquaternium-12, Polyquaternium-13, Polyquaternium-14, Polyquaternium-15, Polyquaternium-16, Polyquaternium-17, Polyquaternium-18, 19, Polyquaternium-20, Polyquaternium-22, Polyquaternium-24, Polyquaternium-27, Polyquaternium-28, Polyquaternium-29, Polyquaternium-30, Polyquaternium-31, Polyquaternium-32, Polyquaternium-33, Polyquaternium-34, Polyquaternium-35, Polyquaternium-36, Polyquaternium-37, Polyquaternium-39, Polyquaternium-43, Polyquaternium-44, Polyquaternium-45, Polyquaternium-46, Polyquaternium-47, Polyquaternium-48, Polyquaternium-49, Polyquaternium-50, Polyquaternium-51, 56, Polyquaternium-57, Polyquaternium-61, Polyquaternium-69, Polyquaternium-86. Polyquaternium-7 is very particularly preferred. The Polyquaternium nomenclature of the cationic polymers used in this application is taken from the declaration of cationic polymers according to the International Nomenclature of Cosmetic Ingredients (INCI declaration) of cosmetic raw materials.

Microcapsules which can be used with preference have mean diameters X _50.3 in the range from 1 to 100 μm, preferably from 5 to 95 μm, in particular from 10 to 90 μm, for example from 10 to 80 μm.

The shell of the microcapsules surrounding the core or (filled) cavity preferably has an average thickness in the range from around 5 to 500 nm, preferably from around 50 nm to 200 nm, in particular from around 70 nm to around 180 nm.

Pearlescent pigments are pigments that have a pearlescent sheen. Pearlescent pigments consist of thin flakes that have a high refractive index and partially reflect light and are partially transparent to light. The pearlescent sheen is created by the interference of the light hitting the pigment (interference pigment). Pearlescent pigments are usually thin flakes of the above-mentioned material, or contain the above-mentioned material as thin multilayer films or as components arranged in parallel in a suitable carrier material.

The pearlescent pigments that can be used according to the invention are either natural pearlescent pigments such as fish silver (guanine / hypoxanthine mixed crystals from fish scales) or mother-of-pearl (from ground mussel shells), monocrystalline, flaky pearlescent pigments such as bismuth oxychloride and pearlescent pigments based on mica / metal oxide. The last-mentioned pearlescent pigments are mica that have been provided with a metal oxide coating.

By using the pearlescent pigments in the suspension according to the invention, gloss and, if appropriate, additional color effects are achieved.

Pearlescent pigments based on mica and based on mica / metal oxide are preferred according to the invention. Mica is one of the layered silicates. The most important representatives of these silicates are muscovite, phlogopite, paragonite, biotite, lepidolite and margarite. To produce the pearlescent pigments in conjunction with metal oxides, the mica, predominantly muscovite or phlogopite, is coated with a metal oxide. Suitable metal oxides include TiO ₂ , Cr ₂ O ₃ and Fe ₂ O ₃ . By appropriate coating, interference pigments and colored luster pigments are obtained as pearlescent pigments according to the invention. In addition to a glittering optical effect, these types of pearlescent pigments also have color effects. Furthermore, the pearlescent pigments which can be used according to the invention can furthermore contain a colored pigment which is not derived from a metal oxide.

The grain size of the pearlescent pigments used with preference is preferably between 1.0 and 100 μm, particularly preferably between 10.0 and 60.0 μm _{, with an average diameter X 50.3 (volume average).}

For the purposes of the invention, speckles are to be understood as meaning macroparticles, in particular macrocapsules, which have an average diameter X _50.3 (volume average) of more than 300 μm, in particular from 300 to 1500 μm, preferably from 400 to 1000 μm.

Speckles are preferably matrix capsules. The matrix is preferably colored. The matrix formation takes place, for example, via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and, like the production of particles with these matrix-forming materials, is well known in the prior art. An exemplary matrix-forming material is alginate. To produce alginate-based speckles, an aqueous alginate solution, which may also contain the active ingredient or ingredients to be included, is dripped and then hardened in a precipitation bath containing ^{Ca 2+} ions or Al ^{3+ ions.} Alternatively, other matrix-forming materials can be used instead of alginate.

The liquid surfactant composition according to the invention can additionally contain further ingredients which further improve the application-related and / or aesthetic properties of the composition depending on the intended use.

The liquid surfactant compositions according to the invention preferably contain at least one enzyme. The enzyme can be a hydrolytic enzyme or another enzyme in a concentration suitable for the effectiveness of the agent. A preferred embodiment of the invention is thus represented by liquid surfactant compositions which comprise one or more enzymes. Preferred enzymes that can be used are all enzymes which can develop a catalytic activity in the agent according to the invention, in particular a protease, amylase, cellulase, hemicellulase, mannanase, tannase, xylanase, xanthanase, xyloglucanase, ß-glucosidase, Pectinase, carrageenase, perhydrolase, oxidase, oxidoreductase or a lipase, as well as mixtures thereof. Enzymes are advantageously contained in the agent in an amount of 1 × 10 ^-8 to 5% by weight, based on the active protein and the total weight of the composition. Increasingly preferred is each enzyme in an amount of 1 × 10 ^-7 -3% by weight, from 0.00001-1% by weight, from 0.00005-0.5% by weight, from 0.0001 to 0.1% by weight and particularly preferably from 0.0001 to 0.05% by weight in liquid surfactant compositions according to the invention, based on active protein. The enzymes particularly preferably show synergistic cleaning performance with respect to certain soiling or stains, ie the enzymes contained in the agent composition mutually support one another in their cleaning performance. Synergistic effects can occur not only between different enzymes, but also between one or more enzymes and other ingredients of the agent according to the invention.

The amylase (s) is preferably an α-amylase. The hemicellulase is preferably a pectinase, a pullulanase and / or a mannanase. The cellulase is preferably a cellulase mixture or a one-component cellulase, preferably or predominantly an endoglucanase and / or a cellobiohydrolase. The oxidoreductase is preferably an oxidase, in particular a choline oxidase, or a perhydrolase.

The proteases used are preferably alkaline serine proteases. They act as unspecific endopeptidases, that is, they hydrolyze any acid amide bonds that are inside peptides or proteins and thereby break down protein-containing soiling on the items to be cleaned. Their pH optimum is usually in the clearly alkaline range. In preferred embodiments, the enzyme contained in the agent according to the invention comprises a protease.

The enzymes used in the present case can be naturally occurring enzymes or enzymes that have been modified on the basis of naturally occurring enzymes by one or more mutations in order to positively influence desired properties, such as catalytic activity, stability or disinfecting performance.

The protein concentration can be determined with the aid of known methods, for example the BCA method (bicinchoninic acid; 2,2'-bichinolyl-4,4'-dicarboxylic acid) or the biuret method. In this regard, the active protein concentration is determined by titrating the active centers using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determining the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 ).

In the liquid surfactant compositions described herein, the enzymes to be used can also be packaged together with accompanying substances, for example from fermentation. In the formulations described, the enzymes are preferably used as liquid enzyme formulation (s).

As a rule, the enzymes are not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations. These ready-made preparations include, for example, solutions of the enzymes, advantageously as concentrated as possible, with little water and / or mixed with stabilizers or other auxiliaries.

• Optional Öle. Unter Ölen sollen hier im Wesentlichen mit Wasser unmischbare Öle verstanden werden. Sie dienen insbesondere zur Anlösung fettiger Anschmutzungen. Es können Alkane eingesetzt werden, bevorzugt sind biologisch abbaubare Öle mit Ether- oder Estergruppen. Auch ist der Einsatz von Terpenen möglich. Bevorzugte Öle sind Dialkylether, mit 6 bis 20 Kohlenstoffatomen in den Alkylresten, insbesondere Dioctylether. Übliche Parfümöle, die mit dem Ziel der Beduftung der Wäsche zugesetzt werden, sollen hier nicht als Ölkomponente im Sinne der Erfindung gewertet werden. In Konzentraten können derartige Öle in Mengen bis zu 60 Gew.-% eingesetzt werden. In bevorzugten Ausführungsformen der Erfindung sind die Zusammensetzungen aber frei von derartigen Ölen.
• Optional Salze. Anorganische Salze sind nicht zwingend erforderlich, um die Mikroemulsionen herstellen zu können. Allerdings sind Konzentrate, insbesondere aniontensidhaltige Konzentrate bevorzugt, welche ein oder mehrere anorganische Salze enthalten. Bevorzugte anorganische Salze sind dabei Alkalimetallsulfate und Alkalimetallhalogenide, insbesondere -chloride, sowie Alkalimetallcarbonate. Ganz besonders bevorzugte anorganische Salze sind Natriumsulfat, Natriumhydrogensulfat, Natriumcarbonat, Natriumhydogencarbonat, Natriumchlorid, Kaliumchlorid und Mischungen aus diesen. Der Gehalt von Zusammensetzungen in Konzentratform an einem oder mehreren anorganischen Salzen beträgt vorzugsweise 20 bis 70 Gew.-%. In den Mikroemulsionen beträgt der Gehalt an einem oder mehreren anorganischen Salzen 0 bis 20 Gew.-% und vorzugsweise 0,01 bis 5 Gew.-%, wobei sich Konzentrationen von 0,1 bis 1 Gew.-% als besonders bevorzugt herausgestellt haben.
• Weitere übliche Waschmittelinhaltsstoffe, allen voran Bleichmittel, Buildersubstanzen, Komplexbildner, wasserlösliche Lösungsmittel, optische Aufheller, Duftstoffe, Stabilisatoren, Rheologiemodifizierer, Farbstoffe etc.

The liquid surfactant compositions according to the invention can furthermore contain:

• Optional oils. Here, oils are essentially to be understood as meaning oils that are immiscible with water. They are used in particular to loosen greasy soiling. Alkanes can be used; preference is given to biodegradable oils with ether or ester groups. The use of terpenes is also possible. Preferred oils are dialkyl ethers with 6 to 20 carbon atoms in the alkyl radicals, in particular dioctyl ethers. Usual perfume oils, which are added with the aim of scenting the laundry, are not to be assessed here as an oil component for the purposes of the invention. Such oils can be used in concentrates in amounts of up to 60% by weight. In preferred embodiments of the invention, however, the compositions are free from such oils.
• Optional salts. Inorganic salts are not absolutely necessary in order to be able to produce the microemulsions. However, concentrates, in particular concentrates containing anionic surfactants, are preferred which contain one or more inorganic salts. Preferred inorganic salts are alkali metal sulfates and alkali metal halides, in particular chlorides, and also alkali metal carbonates. Very particularly preferred inorganic salts are sodium sulfate, sodium hydrogen sulfate, sodium carbonate, sodium hydrogen carbonate, sodium chloride, potassium chloride and mixtures of these. The content of one or more inorganic salts in compositions in concentrate form is preferably 20 to 70% by weight. The content of one or more inorganic salts in the microemulsions is 0 to 20% by weight and preferably 0.01 to 5% by weight, concentrations of 0.1 to 1% by weight having proven to be particularly preferred.
• Other common detergent ingredients, above all bleaches, builders, complexing agents, water-soluble solvents, optical brighteners, fragrances, stabilizers, rheology modifiers, dyes, etc.

The liquid surfactant composition according to the invention can contain, as further usual detergent ingredients, in addition to the above-mentioned at least one, preferably two or more other ingredients selected from the following group: builders, bleaches, electrolytes, non-aqueous but water-miscible solvents, pH adjusters, perfumes, Perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, anti-seizure agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, anti-aging agents, anti-aging agents, anti-slip agents, anti-slip agents, anti-slip agents, anti-slip agents, anti-slip agents, anti-swelling agents, anti-slip agents, anti-swelling agents, anti-slip agents, anti-swelling agents, anti-swelling agents, anti-swelling agents, anti-swelling agents, anti-redeposition agents, anti-redeposition agents, anti-redeposition agents , softening components and UV absorbers.

Builders that may be contained in the detergent composition include, in particular, silicates, aluminum silicates (especially zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Organic builders which can be present in the detergent composition are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function. For example, these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. Aminopolycarboxylic acids, such as, in particular, glutamine diacetic acid (GLDA) and methylglycinediacetic acid (MGDA) and their salts are also suitable.

Polymeric polycarboxylates are also suitable as builders. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 600 to 750,000 g / mol. Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 1,000 to 15,000 g / mol. Because of their superior solubility, the short-chain polyacrylates from this group, which have molar masses from 1,000 to 10,000 g / mol, and particularly preferably from 1,000 to 5,000 g / mol, can be preferred.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. To improve the water solubility, the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

In the liquid detergents, however, soluble builders such as citric acid or acrylic polymers with a molar mass of 1,000 to 5,000 g / mol are preferably used.

Non-aqueous solvents which are miscible with water can be added to the liquid surfactant composition of the present invention. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines or glycol ethers. For example, the solvents are selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol ether, butyl glycol ether, diethylene glycol ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxy triglycol, ethoxy triglycol, butoxy triglycol, 1-butoxyethoxy-2-propanol, and these mixtures of these solvents.

The liquid surfactant compositions according to the invention can also be formulated in various embodiments in the form of single-use portions. These include in particular containers made of water-soluble materials which are filled with the concentrates according to the invention. Single-chamber or multi-chamber containers, especially made of polyvinyl alcohol or polyvinyl alcohol derivatives or copolymers with vinyl alcohol or vinyl alcohol derivatives as monomer, are particularly preferred. These disposable portions ensure that the correct amount of the concentrate according to the invention for the creation of the microemulsion system and for the corresponding performance associated therewith is used in the first underwash cycle. If necessary, depending on the amount of the textile or item of laundry to be washed, several single servings can also be used.

1. a) auf eine Temperatur T2 erwärmte Stoffe vermischt werden mit einer Mikroemulsion des ersten Erfindungsgegenstandes bei einer Temperatur T3 und
2. b) anschließend die Mischung auf eine Temperatur T4 abgekühlt wird,

wobei die Temperaturen T2 und T3 wenigstens so hoch wie der Schmelzpunkt mindestens eines besagten nicht-polymeren, organischen Verdickungsmittels der Mikroemulsion sind und die Temperatur T4 unter dem Schmelzpunkt der besagten nicht-polymeren, organischen Verdickungsmittel liegt.A fourth subject matter of the invention is a method for producing a liquid surfactant composition, in particular a detergent, wherein

1. a) substances heated to a temperature T2 are mixed with a microemulsion of the first subject matter of the invention at a temperature T3 and
2. b) then the mixture is cooled to a temperature T4,

wherein the temperatures T2 and T3 are at least as high as the melting point of at least one said non-polymeric, organic thickening agent of the microemulsion and the temperature T4 is below the melting point of said non-polymeric, organic thickening agents.

A liquid surfactant composition of the third aspect of the invention is obtained by this production method.

The preferred features of the first subject of the invention (e.g. thickener according to the invention, the surfactant system according to the invention and the additional emulsion features (fishtail point, emulsion structure, etc.) also apply mutatis mutandis to the fourth subject of the invention.

A preferred method for producing a liquid surfactant composition is characterized in that at least one said, non-polymeric, organic thickener of the microemulsion at 1013 mbar has a melting point of a maximum of 90 ° C, preferably a maximum of 85 ° C, particularly preferably a maximum of 80 ° C. It is preferred according to the invention if the said thickener has a melting point of between 30 ° C and 100 ° C, in particular between 40 ° C and 95 ° C, very particularly preferably from 60 ° C to 90 ° C.

A preferred method for producing a liquid surfactant composition is characterized in that the substances heated to temperature T2 contain water, at least one surfactant or mixtures thereof. It is again preferred if pure water is not mixed with the said microemulsion as the first substance. If water is to be added as the first substance, then only in a defined amount, so that the microemulsion according to the invention is initially retained in the mixture. Particularly preferably, surfactants are first mixed as a substance with the said microemulsion and then water, or a mixture of surfactant and, based on the weight of this mixture, water in an amount of at most 50% by weight.

The microemulsion used in the process for producing a liquid surfactant composition was preferably produced by a process of the second subject matter of the invention.

• Temperatur T1 ≥ Temperatur T3 ist,
• T3 wenigstens so hoch wie der Schmelzpunkt mindestens eines besagten nicht-polymeren, organischen Verdickungsmittels der Mikroemulsion ist,
• und die erhaltene Mikroemulsion mit der Temperatur T3 in Schritt a) des Verfahrens eingebracht wird.

In a process for producing a liquid surfactant composition, the microemulsion is preferably produced by a process of the second subject matter of the invention prior to step a) and the microemulsion produced in this way, which is still kept at temperature T1, is brought to a temperature T3, with the proviso that

• Temperature T1 ≥ temperature T3,
• T3 is at least as high as the melting point of at least one said non-polymeric, organic thickener of the microemulsion,
• and the microemulsion obtained is introduced with the temperature T3 in step a) of the process.

In another preferred embodiment, T3 is at least as high as the highest melting point of the said non-polymeric, organic thickening agent used in the microemulsion.

The mixture is preferably cooled to temperature T4 gradually. The temperature T4 is preferably at least 10 K below the lowest melting point of the thickeners according to the invention used. Temperature T4 is preferably at most 40 ° C., in particular at most 30 ° C., very particularly preferably room temperature.

The cooling process can preferably be carried out by adding water at a temperature <T4. The water used for cooling can also contain further ingredients of the surfactant compositions according to the invention.

Particulate solids are preferably mixed with and suspended during cooling or after cooling to temperature T4.

In addition, additives can also be mixed in after cooling to T4.

Examples

Production of the microemulsion according to the invention (microemulsion premix 1):
A microemulsion according to the invention was produced using the following method:
0.45g Hydrogenated Castor Oil (HCO) was mixed with 0.134g dioctyl sulfosuccinate sodium salt (AOT - AS: 97%) and 0.15g a-alkyl polyglycol ether (Marlox RT 42 - AS: 100%, Sasol) in 0.045g H2O and added to 90 ° C melted to obtain a first transparent microemulsion.

The microemulsion obtained in this way, which has not been cooled, is used to produce the liquid surfactant compositions of Examples 1 to 3.

Example 1:

General description of the mix of microemulsion premix with liquid detergent matrix:
A defined amount of the microemulsion premix according to the invention is heated to the desired production temperature (see Example 3). The amount is selected so that a desired amount of HCO is present in the finished mixture. At the manufacturing temperature, the components of the liquid detergent matrix are gradually added to the microemulsion premix. The amphiphilic components (surfactants) are preferably added first and homogenized. These amphiphilic components can either be used as a stock solution with water or pure. The mixture is further homogenized and kept at the desired temperature. The pH is also adjusted at the same time. The mixture is then gradually cooled to room temperature with subsequent addition of temperature-sensitive components (enzymes, perfume, pigment). The cooling does not cause any shift in the previously set pH value. The production process works at least as well, even better, if the amphiphilic components of the liquid detergent matrix are brought to the desired production temperature and the desired amounts of the microemulsion premices according to the invention are mixed with them homogeneously. During the homogenization of the amphiphilic components of the liquid detergent matrix with the microemulsion premices according to the invention, it is preferable to ensure that the desired production temperature is kept constant. Table 1: Liquid surfactant composition Chemical name % Active substance in the formula stabilizer 1.06 citric acid 2.34 Antifoam additive 0.04 C12-18 fatty alcohol ether sulfate with 2 EO 7.42 C12-18 fatty alcohol with 7 EO 5.82 C10-13 alkylbenzenesulfonic acid 5.82 NaOH 2.47 Glycerin 2.66 Complex images 0.53 Preservatives 0.06 Ethanol 1.32 from microemulsion 1 (premix): Hydrogenated castor oil (HCO) l 0.90 Dioctyl Sodium Sulphosuccinate 0.26 Alkyl polyglycol ethers * 0.30 Temperature sensitive components: Enzymes 0.90 Perfume 0.78 pigment 0.001 Water, ad. 100% * Active ingredient from the raw material Marlox RT 42 ^® (Sasol).

This formulation is stable and shows no evidence of instability. The resulting flow limit of this liquid detergent matrix mixed with premix microemulsion is 0.3 Pa. Visible beads can be suspended in bulk and evenly distributed. An analogous formulation without HCO is unstable (a liquid phase separation can be observed), has no flow limit (0.0 Pa), the beads sink and accumulate at the bottom of the bottle.

The same formulation mixed with the HCO-containing premices EP 1 502 646 B1 and WO 2015/200062 A1 do not show any of the results described above. The HCO that has crystallized out is in an undissolved state in the bulk in the form of one or more white, solid lumps as larger agglomerates on the bottom. There is no flow limit (0.0 Pa). The visible beads sink to the bottom of the bottle and accumulate there.

Example 2:

Table 2: Liquid surfactant composition according to the invention Chemical name % Active substance in the formula stabilizer 1.12 citric acid 3.58 Antifoam additive 0.05 C12-18 fatty alcohol ether sulfate with 2 EO 10.07 C12-18 fatty alcohol with 7 EO 7.84 C10-13 alkylbenzenesulfonic acid 7.84 NaOH 3.47 1,2 propanediol 6.38 Complex images 0.78 Texcare SRN 170 1.46 Ethanol 2.24 from microemulsion 1 (premix): Hydrogenated castor oil (HCO) 0.90 Dioctyl Sodium Sulphosuccinate 0.26 Alkyl polyglycol ethers * 0.30 Temperature sensitive components Optical brightener 0.11 Enzymes 1.86 Perfume 1.01 pigment 0.01 Water, ad. 100% * Active ingredient from the raw material Marlox RT 42 ^® (Sasol).

This formulation is stable and shows no signs of instability. The resulting flow limit of this liquid detergent matrix mixed with premix microemulsion is 1.7 Pa. Visible beads can be suspended in bulk and evenly distributed. An analogous formulation without HCO is unstable (a liquid phase separation can be observed) and has no flow limit (0.0 Pa). The beads sink and accumulate at the bottom of the bottle.

The same formulation mixed with the HCO-containing premices EP 1 502 646 B1 and WO 2015/200062 A1 did not show any of the results described above. The crystallized HCO is in an undissolved state in the bulk in the form of one or more white, solid lumps as larger agglomerates on the ground. There is no flow limit (0.0 Pa). The visible beads sink to the bottom of the bottle and accumulate there.

Example 3:

Table 3: Correlation between production temperature and resulting yield point based on results obtained from Example 1. Manufacturing temperature [° C] Resulting yield point [Pa] 90 0.82 80 0.90 75 1.30

The use of premixes according to the invention always leads to the formation of a flow limit. These results show a relationship between the production temperature during the production process of the liquid detergent formulation and the intensity of the resulting yield points. In this way, the values of the flow limits of the liquid detergents can be set in a targeted manner.

Claims (15)

1. A microemulsion, containing, in each case based on the total weight of the emulsion,

   a) a liquid phase,

   b) a total amount of from 30.0 wt.% to 95.0 wt.% of at least one non-polymeric, organic thickener having a molecular weight in the range of from 100 g/mol to 1500 g/mol as the emulsified phase,

   c) a total amount of from 2.0 wt.% to 60.0 wt.% of a surfactant system containing at least one non-ionic surfactant.
2. The microemulsion according to claim 1, characterized in that said thickener is in the oil-rich phase of the microemulsion.
3. The microemulsion according to claim 1 or 2, characterized in that the liquid phase and the emulsified phase are present as bicontinuous phases or as layers of an L_α phase, in particular as bicontinuous phases.
4. The microemulsion according to one of the preceding claims, characterized in that the surfactant system has a fishtail point in the range of from 0.01 wt.% to 80 wt.%, preferably 0.1 wt.% to 70 wt.%, particularly preferably 0.2 wt.% to 60 wt.%.
5. The microemulsion according to one of the preceding claims, characterized in that the fishtail point is in the range of from 0.01 to 80 wt.% total surfactant and 0.01 to 50 wt.% surfactant C2, preferably 0.1 to 70 wt.% total surfactant and 0.01 to 40 wt.% surfactant C2, most preferably 0.2 to 60 wt.% total surfactant and 0.1 to 35 wt.% surfactant C2.
6. The microemulsion according to one of the preceding claims, characterized in that the mean curvature of the amphiphilic film in the single-phase region of the microemulsion is 0 in the temperature range of from 0 to 100 °C, preferably 40 to 98 °C, more preferably 60 to 95 °C.
7. The microemulsion according to one of the preceding claims, characterized in that the total amount of said thickener is at least 40 wt.%.
8. The microemulsion according to one of the preceding claims, characterized in that said at least one low-molecular-weight, organic thickener is selected from hydrogenated castor oil, 12-hydroxyoctadec-9-anoic acid, 12-hydroxystearic acid, a glyceride having at least two 12-hydroxyoctadec-9-anoic acid functional groups, triricinolein, a glyceride having at least two 12-hydroxystearic acid functional groups, tris-12-hydroxystearin, 4,6-O-benzylidene monosaccharide, C₈-C₂₂ alkylamide derivatives of D-glucosamine, urea derivatives, gemini surfactants (in particular N-lauroyl-L-lysine ethyl ester), or mixtures thereof.
9. The microemulsion according to one of the preceding claims, characterized in that at least one C_8-20 alkyl ether, preferably at least one C_8-20 fatty alcohol alkoxylate having 1 to 10 EO and 0 to 10 PO, is contained as the non-ionic surfactant.
10. The microemulsion according to one of the preceding claims, characterized in that the surfactant system additionally contains at least one anionic surfactant.
11. The microemulsion according to claim 10, characterized in that the at least one anionic surfactant is selected from C₉-C₁₅ alkylbenzene sulfonate, C₁₀-C₂₀ alkyl ether sulfate having 2 to 10 units of alkylene oxide, dialkyl sulfosuccinate of formula (I) or combinations thereof,

    

    the functional groups R¹ and R², independently of one another, each being linear or branched and containing 6 to 22 carbon atoms, preferably 6 to 12 carbon atoms, and particularly preferably being selected from 1-hexyl, 3,5,5-trimethyl-1-hexyl, 2-ethyl-1-hexyl, 6-methyl-1-heptyl, 2-methyl-1-heptyl, 2-propyl-1-pentyl, 2,4,4-trimethyl-1-pentyl, 1-ethyl-2-methyl-1-pentyl, and 1,4-dimethyl-1-hexyl, and 1/n Mⁿ⁺ being an equivalent of an n-valent cation.
12. The microemulsion according to one of the preceding claims, characterized in that the total amount of said surfactant is from 2 wt.% to 50 wt.%.
13. A method for preparing a microemulsion existing at a temperature T1, in which

    i) based on the weight of the microemulsion, a total amount of from 10 wt.% to 99.0 wt.% of at least one non-polymeric, organic thickener having a molecular weight of from 100 g/mol to 1500 g/mol as the first liquid phase is mixed with at least one liquid as the second liquid phase, at least one surfactant C1 and at least one surfactant C2, thus producing a cloudy mixture, and

    ii) the mixture is brought to a temperature T1 and further mixed thoroughly,

    with the proviso that the temperature T1 is at least as high as the melting point of at least one said non-polymeric, organic thickener from step i) and a microemulsion is obtained.
14. A liquid surfactant composition, in particular a washing agent, which is obtained by mixing a total amount, based on the total weight of the liquid surfactant composition, of from 0.001 wt.% to 5 wt.% of at least one microemulsion according to one of claims 1 to 9 with a composition containing water and at least one surfactant, with the proviso that the liquid surfactant composition has

    - a total amount of from 5 to 80 wt.% of at least one surfactant and

    - a yield point, preferably of from 0.001 to 6 Pa, at 20 °C.
15. A method for preparing a liquid surfactant composition, in particular a washing agent, wherein

    a) substances heated to a temperature T2 are mixed with a microemulsion according to claims 1 to 12 at a temperature T3, and

    b) the mixture is subsequently cooled to a temperature T4,

    wherein the temperatures T2 and T3 are at least as high as the melting point of at least one said non-polymeric, organic thickener of the microemulsion and the temperature T4 is below the melting point of said non-polymeric, organic thickener.